CA2001174A1 - Development of radiation sensitive compositions - Google Patents

Development of radiation sensitive compositions

Info

Publication number
CA2001174A1
CA2001174A1 CA 2001174 CA2001174A CA2001174A1 CA 2001174 A1 CA2001174 A1 CA 2001174A1 CA 2001174 CA2001174 CA 2001174 CA 2001174 A CA2001174 A CA 2001174A CA 2001174 A1 CA2001174 A1 CA 2001174A1
Authority
CA
Canada
Prior art keywords
developer liquid
sodium
composition
radiation sensitive
developer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2001174
Other languages
French (fr)
Inventor
Michael Ingham
Paul Anthony Styan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CA 2001174 priority Critical patent/CA2001174A1/en
Publication of CA2001174A1 publication Critical patent/CA2001174A1/en
Abandoned legal-status Critical Current

Links

Landscapes

  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

ABSTRACT
Development of Radiation Sensitive Compositions Image-wise exposed radiation sensitive compositions are processed using a developer liquid comprising an ethyl hexyl sulphate. The developer liquid may additionally include a surface active agent such as a polyoxyethylene lauryl ether or an ethylene oxide/propylene oxide condensate of poly(ethylene) glycol, an alkaline material such as sodium metasilicate, a water soluble carboxylic acid salt such as sodium octanoate, and the sodium salt of ethylene diamine tetra acetic acid. Such developer liquids can be formulated for use with either positive-working or negative-working plates.

Description

Z~)03L17~

DEVELOPMENT OF RADIATION SENSITI~E
COMPOSITIONS
This invention relates to the development of radiation-sensitive compositions and is concerned with the development of such compositions as are used for the production of printing plates and photoresists.
In the production of printing plates and photoresists, a radiation sensitive composition is coated onto a substrate to form a radiation sensitive plate which is then image-wise exposed to radiation so as to selectively expose different areas of the coating. The radiation struck areas and non-radiation struck areas have differing solubility in developer liquids and thus the more soluble areas can be selectively removed from the substrate by the application of a suitable developer liquid to leave an image on the substrate constituted by the less soluble areas.
Radiation sensitive compositions are usually classified as being either positive-working or negative-working. Positive-working compositions have the property of becoming more soluble in a given developer liquid when exposed to radiation whereas negative-working compositions have the property of becoming less soluble.
This difference has meant that in the past, the developer liquids used for the two classes of composition have been substantially different. In particular, negative-working compositions have generally required a developer liquid comprising a substantial proportion of an organic solvent. Thus a developer liquid suitable for positive-working compositions would not develop a negative-working composition and a developer liquid suitable for a negative-working composition would over develop a 200~4 positive-working composition.
It is an object of the present invention to provide a developer liquid suitable for use in developing both positive and negative-working compositions.
According to one aspect of the present invention there is provided a method of developing an image-wise exposed radiation sensitive composition which comprises the step of contacting the composition with a developer liquid containing an ethylhexyl sulphate.
According to another aspect of the present invention there is provided a developer liquid comprising, an alkaline material, an ethylhexyl sulphate, and a surface active agent.
The developer liquid can be used with either positive-working compositions such as compositions comprising a quinone diazide and an alkali soluble resin, compositions comprising a diazo ester and a novolak resin, and compositions comprising a novolak ester or negative-working compositions such as compositions comprising a diazo compound containing groups having the structure y A-N2~ - Ar - R - X - C - X' in which Ar represents a divalent or other polyvalent radical derived from an aromatic or heteroaromatic compound; X and X' which may be the same or different, each represents O, S or an imino group, provided that at least one of X and X' is an imino group; Y
represents O or S; R represents a single bond or a divalent or other polyvalent radical; and A- is an anion tas described in EP-A-0030862 which is herein incorporated by reference), compositions comprising at least one photoinitiator and at least one Z()O~

photopolymerisable compound which is an acrylic or methacrylic ester of a tetra functional polyol having the general formula:
C(CH2O)4(c3H6O)n H4 wherein the average degree of propoxylation n is from 3 to 6, from 50% to 90% of the available hydroxy groups have been converted to acrylate or methacrylate groups, and the remaining hydroxy groups have been reacted with a di-isocyanate or a polyisocyanate (as described in EP-A-0260823 which is herein incorporated by reference), compositions comprising a thioxanthone sensitiser and a light sensitive polymer having pendant dimethyl maleimide groups, compositions comprising supported diazodiphenylamine/formaldehyde condensate, and compositions comprising trimethylolethane triacrylate and a methyl methacrylatetmethacrylic acid copolymer as binder.
The developer liquid is particularly suitable for use in machines for automatically developing radiation sensitive plates including such compositions.
Generally, the developer liquid can be used in any processor designed for developing positive-working plates. The useful life of the developer liquid will depend on the manner in which the development section of the processor is constructed. Processors having fully enclosed development tanks will give greater bath life due to restricted contact of the developer liquid with the atmosphere. The activity of the developer liquid can be maintained by replenishment and monitored by determining its conductivity as described in EP-A-0107454.
The alkaline material is the primary developing agent for positive-working compositions and its concentration determines the degree of development and the useful life of the developer liquid. The ~)1)1174 alkaline material may be a hydroxide, a phosphate an amine, such as monoethanolamine or a silicate and preferably is sodium metasilicate. In the latter case, the sodium metasilicate concentration will generally be from 4 to 20wjv% preferably from 7 to 12 w/v%.
Suitable hydroxide concentrations are 0.2 to 10 w/v%
(preferably from 2.0 to 5.0 w/v%), suitable phosphate co~centrations are 4 to 20w/v% (preferably 7 to 12w/v%), and suitable amine concentrations are 1 to 20 v/v%
(preferably 5 to 10 v/v%).
The ethyl hexyl sulphate acts as a developing aid for negative working compositions and is preferably in the form of the sodium salt. However, other salts may be used. Generallv its concentration will be from 2 to 20% by vol, preferably from 3 to 5% by vol, of a 40w/v% solution.
The surface active agent prevents overdevelopment of positive working compositions and may be a non-ionic surfactant such as a polyoxyethylene lauryl ether or an ethylene oxide/propylene oxide condensate of polv~ethylene) glycol. The latter is preferred since it also prevents soiliny deposits being formed on the plate surface when developing radiation sensitive plates in some automatic plate processors using hard water in their plate washing section.
Generally the surface active agent will be present in an amount of from 0.075% to 1.5% by vol, preferably from 0.2 to 0.5% by vol.
In an embodiment, the developer additionally includes a water soluble salt of an aliphatic carboxylic acid. This may be the potassiurn or sodium salt of an acid containing 1 9 carbon atoms, preferably octanoic acid. It acts as a developing aid for both positive and negative-working compositions. The use of sodium octanoate is preferred. The water soluble salt 20~174 will generally be present in an amount of from 1% to 20% by vol, preferably from 2% to 6% by vol, of a 40%
w/v solution.
In an embodiment, the developer additionally includes the sodium salt of ethylene diamine tetraacetic acid. This has the advantage of complexing calcium and magnesium ions present in the wash water to prevent the formation of hard water salts. It will generally be present in an amount of from .2% to 10.0w/v%, preferably 1 to 3w/v%.
The following Examples illustrate the invention A series of positive-working pre-sensitised plates consisting of a grained and anodised aluminium substrate coated with a composition based on a quinone diazide and an alkali soluble novolak resin were exposed in a printing down frame beneath a continuous tone step-wedge.
The plates were then processed in a Howson-Algraphy Positive Plate Processor containing in the developer section a developer solution having the formulation:-25 Sodium metasilicate 3.5Kg Brij 30 0.25L
Rewopol NEHS-40 5L
Sodium octanoate solution (40% w/w) 5L
Nervanaid BConc. 1.0 Kg Water to 5OL
Rewopol NEHS-40 is a 40% solution of the sodium salt of 2-ethyl hexyl sulphate tn - ethyl hexyl sulphate) produced by Rewo Chemicals Ltd, Nervanaid B
Conc is the sodium salt of ethylene diamine tetraacetic 20011~

acid (ABM Chemicals Ltd), and ~rij 30 (I.C.I.) is a polyoxyethylene lauryl etherO
There was no sign of the plate being over developed.

A series of negative-working plates were made according to Example 1 of European Patent Specification No.0030862 and were exposed and processed in the same wa~ as the plate of Example 1. The plates developed cleanly.

Example 2 was repeated except that plates made according to Example 1 of European Patent Specification No.0260823 were used.
Similar results were obtained.

Examples 1 to 3 were repeated using, as the developer, the following composition:-Nervanaid B Conc 0.25 Kg Sodium metasilicate 3.50 Kg Sodium octanoate (40%) 2.50L
Rewopol NEHS 40 5.00L
Brij 30 0.25L
Water to 50L
Similar results were obtained in each case.

Examples 1 to 3 were repeated using as the developer, the following composition:-Nervanaid B conc 20Kg Sodium metasilicate (5H20) 7OKg Sodium octanoate (40%) 100L
Rewopol NEHS 40 100L
Supronic B10 2L
Demineralised water to 1 OOOLo 2001~

Supronic B10 is an ethylene oxide/propylene oxide copolymer of poly(ethylene glycol).
Similar results were obtained in each case.

Examples 1 to 3 were repeated using as the dev~loper the following composition:-Nervanaid B conc. 2OKg Sodium metasilicate (5H2O) 70Kg Sodium octanoate (40%) 10OL
Rewopol NEHS 40 100L
Supronic B10 0.75L
Demineralised water to 1000L.
Similar results were obtained in each case.

The following developer formulation was used in an Autopos automatic plate processor to develop an image-wise exposed Super Amazon Plate (Howson-Algraphy) including a positive working radiation sensitive composition based on a diazo ester and a novolak resin:-Sodium Metasilicate 70Kg Brij 30 5L
Rewopol NEHS40 10OL
Sodium Octanoate (40% sol) 100L
Nervanaid B Conc 2OKg Demineralised Water to 1000L
The plate developed cleanly with no sign of over-development.
Similar results were obtained using a Super Spartan Plate (Howson-Algraphy) and a Triton Plate (Howson-Algraphy~ which are similarly based on positive working diazo ester/novolak compositions.

The above formulation was used to develop negative-working AQ2 and AQ3 plates ~Howson-Algraphy) ~oo~

including radiation sensitive compositions based on a diazo resin and binder.
The plates developed cleanly with no residual coating.
EXAMPLES 11 to 15 Examples 9 and 10 were repeated using the following developer formulations:

Sodium Metasilicate70Kg 40Kg70Kg 70Kg 70Kg Brij 30 15L 5L 5L 5L 5L
Rewopol NEHS-40100L 100L 50L100L 100L
Sodium Octanoate (40% sol)100L100L 100L 50L 100L
Nervanaid B Conc20Kg20Kg 20Kg20Kg 40Kg Demineralised Water to 1000L 1000L 1000L 1000L 1000L
In each case, the plates developed cleanly.

Examples 9 and 10 were repeated using the following developer formulations:-Sodium Metasilicate 70Kg 70Kg Supronic B10 0.75L 2L
Rewopol NEHS-4010OL 10OL
Sodium Octanoate t40% sol)100L 100L
Nervanaid B Conc20Kg 20Kg Demineralised water to 1000 L 1000 L
The plates developed cleanly in each case~

Example 9 was repeated using commercially available positive working plates viz New Capricorn (Horsell) including a radiation sensitive composition based on novolak ester, P61 (Hoechst) including a radiation sensitive composition based on a diazo ester 20011~7~

and novolak resin and Nylolith PMS (BASF) including a radiation sensitive composition based on a novolak ester. These plates processed cleanly with no over-development.

Example 9 was repeated using Nylolith NL (a commercially available negative working plate of BASF
including a radiation sensitive composition based on a supported diazo system). It developed cleanly~

The developer formulation of Example 9 was used in an NP60 processor (Horsell) to develop AQ3, Super Amazon and Super Spartan plates and was used in a VA6 processor (Hoechst) to develop AQ3 and Super Amazon plates and an Ultrapos (Horsell) plate including a radiation sensitive composition based on a novolak ester. In all cases it was found to develop both negative and positive plates cleanly.

Claims (15)

1. A method of developing an image-wise exposed radiation sensitive composition which comprises the step of contacting the composition with a developer liquid containing an ethyl hexyl sulphate.
2. A method according to claim 1 wherein the composition is a positive working composition.
3. A method according to claim 2 wherein the composition comprises a quinone diazide and an alkali soluble resin.
4. A method according to claim 1 wherein the composition is a negative working composition.
5. A method according to claim 4 wherein the composition comprises a diazo compound containing groups having the structure A-N2+ - Ar - R - X - ? - X' -in which Ar represents a divalent or other polyvalent radical derived from an aromatic or heteroaromatic compound; X and X' which may be the same or different, each represents O, S or an imino group, provided that at least one of X and X' is an imino group; Y
represents O or S; R represents a single bond or a divalent or other polyvalent radical; and A- is an anion.
6. A method according to claim 4 wherein the composition comprises at least one photoinitiator and at least one photopolymerisable compound which is an acrylic or methacrylic ester of a tetra functional polyol having the general formula:
C(CH2O)4(C3H6O)n H4 wherein the average degree of propoxylation n is from 3 to 6, from 50% to 90% of the available hydroxy groups have been converted to acrylate or methacrylate groups, and the remaining hydroxy groups have been reacted with a di-isocyanate or a polyisocyanate.
7. A method according to claim 1 wherein the radiation sensitive composition is in the form of a coating on a substrate.
8. A developer liquid comprising an alkaline material, an ethyl hexyl sulphate, and a surface active agent.
9. A developer liquid as claimed in claim 8 wherein the alkaline material is sodium metasilicate.
10. A developer liquid as claimed in claim 8 wherein the surface active agent is a polyoxyethylene lauryl ether or an ethylene oxide/propylene oxide concentrate of poly(ethylene) glycol.
11. A developer liquid as claimed in claim 8, which additionally includes a water soluble salt of an aliphatic carboxylic acid.
12. A developer liquid as claimed in claim 11 wherein the water soluble salt is the sodium or potassium salt of an acid containing 1 to 9 carbon atoms.
13. A developer liquid as claimed in claim 12 wherein the acid is octanoic acid.
14. A developer liquid as claimed in claim 8 which additionally includes the sodium salt of ethylene diamine tetra acetic acid.
15. A developer liquid as claimed in claim 8 comprising from 4 to 20 w/v% of sodium metasilicate, from 0.075 to 1.5v/v% of surface active agent, from 1 to 20 v/v% of a 40w/v% solution of sodium octanoate, from 2 to 20v/v% of a 40w/v% solution of sodium ethyl hexyl sulphate, and up to 10.0w/v% of the sodium salt of ethylene diamine tetra acetic acid.
CA 2001174 1989-10-20 1989-10-20 Development of radiation sensitive compositions Abandoned CA2001174A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CA 2001174 CA2001174A1 (en) 1989-10-20 1989-10-20 Development of radiation sensitive compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CA 2001174 CA2001174A1 (en) 1989-10-20 1989-10-20 Development of radiation sensitive compositions

Publications (1)

Publication Number Publication Date
CA2001174A1 true CA2001174A1 (en) 1991-04-20

Family

ID=4143372

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2001174 Abandoned CA2001174A1 (en) 1989-10-20 1989-10-20 Development of radiation sensitive compositions

Country Status (1)

Country Link
CA (1) CA2001174A1 (en)

Similar Documents

Publication Publication Date Title
EP0080042B1 (en) Method for the development of photoresist layers, and developer
US4469776A (en) Developing solution for light-sensitive printing plates
US4885230A (en) Burn-in gumming composition for offset printing plates
CA1251678A (en) Aqueous-alkaline solution and process for developing positive-working reproduction layers
EP1103859B1 (en) Developing composition for alkaline-developable lithographic printing plates with different interlayers
GB2068136A (en) Developers for lithographic printing plates
CA1184803A (en) Developing diazonium salt polycondensation product layers using a developer composition containing a salt of substituted aromatic carboxylic acid
CA1189376A (en) Developer for positive photolithographic articles including sodium silicate and sodium chloride
EP0366321B1 (en) Development of radiation sensitive compositions
JPH01282549A (en) Composition of developing solution for planographic printing plate and developing process
US5278030A (en) Developer solution comprising ethyl hexyl sulphate, a surfactant, an alkaline material and having a pH of not less than 12
US4968584A (en) Method for making lithographic printing plate
US4366224A (en) Inorganic lithium developer composition
CA2001174A1 (en) Development of radiation sensitive compositions
JPH03101735A (en) Method for processing photosensitive planographic printing plate
JPH02254457A (en) Developing solution composition for photosensitive planographic printing plate and photomechanical process
JPH0355816B2 (en)
JPH11352700A (en) Alkaline developer for photoresist
JPS62175758A (en) Developer composition for photosensitive lithographic printing plate
JP2000171984A (en) Development of radiation sensitive composition
JPH0428295B2 (en)
JP2001125281A (en) Developing solution composition
JP2733952B2 (en) Developer composition
WO1990003275A1 (en) Baking treatment of lithographic printing plate
US4937170A (en) Coupling agents for photographic elements

Legal Events

Date Code Title Description
EEER Examination request
FZDC Correction of dead application (reinstatement)
FZDE Dead